Aromatic hydrocarbon(s), particularly benzene, toluene, ethylbenzene and xylenes, are important commodity chemicals in the petrochemical industry. Currently, aromatics are most frequently produced from petroleum-based feedstocks by a variety of processes, including catalytic reforming and catalytic cracking. However, as the world supplies of petroleum feedstocks decrease, there is a growing need to find alternative sources of aromatic hydrocarbon(s).
One possible alternative source of aromatic hydrocarbon(s) is methane, which is the major constituent of natural gas and biogas. World reserves of natural gas are constantly being upgraded and more natural gas is currently being discovered than oil. Because of the problems associated with transportation of large volumes of natural gas, most of the natural gas produced along with oil, particularly at remote places, is flared and wasted. Hence the conversion of alkanes contained in natural gas directly to higher hydrocarbon(s), such as aromatics, is an attractive method of upgrading natural gas, providing the attendant technical difficulties can be overcome.
A large majority of the processes currently proposed for converting methane to liquid hydrocarbon(s) involve initial conversion of the methane to synthesis gas, a blend of H2 and CO. However, production of synthesis gas is capital and energy intensive and hence routes that do not require synthesis gas generation are preferred.
A number of alternative processes have been proposed for directly converting methane to higher hydrocarbon(s). One such process involves catalytic oxidative coupling of methane to olefins followed by the catalytic conversion of the olefins to liquid hydrocarbon(s), including aromatic hydrocarbon(s). For example, U.S. Pat. No. 5,336,825 discloses a two-step process for the oxidative conversion of methane to gasoline range hydrocarbon(s) comprising aromatic hydrocarbon(s). In the first step, methane is converted to ethylene and minor amounts of C3 and C4 olefins in the presence of free oxygen using a rare earth metal promoted alkaline earth metal oxide catalyst at a temperature between 500° C. and 1000° C. The ethylene and higher olefins formed in the first step are then converted to gasoline range liquid hydrocarbon(s) over an acidic solid catalyst containing a high silica pentasil zeolite.
However, oxidative coupling methods suffer from the problems that they involve highly exothermic and potentially hazardous methane combustion reactions and they generate large quantities of environmentally sensitive carbon oxides.
A potentially attractive route for upgrading methane directly into higher hydrocarbon(s), particularly ethylene, benzene and naphthalene, is dehydroaromatization or reductive coupling. This process typically involves contacting the methane with a catalyst comprising a metal, such as rhenium, tungsten or molybdenum, supported on a zeolite, such as ZSM-5, at high temperature, such as 600° C. to 1000° C. Frequently, the catalytically active species of the metal is the zero valent elemental form or a carbide or oxycarbide.
For example, U.S. Pat. No. 4,727,206 discloses a process for producing liquids rich in aromatic hydrocarbon(s) by contacting methane at a temperature between 600° C. and 800° C. in the absence of oxygen with a catalyst composition comprising an aluminosilicate having a silica to alumina molar ratio of at least 5:1, said aluminosilicate being loaded with (i) gallium or a compound thereof and (ii) a metal or a compound thereof from Group VIIB of the Periodic Table.
In addition, U.S. Pat. No. 5,026,937 discloses a process for the aromatization of methane which comprises the steps of passing a feed stream, which comprises over 0.5 mole % hydrogen and 50 mole % methane, into a reaction zone having at least one bed of solid catalyst comprising ZSM-5, gallium and phosphorus-containing alumina at conversion conditions which include a temperature of 550° C. to 750° C., a pressure less than 10 atmospheres absolute (1000 kPa-a) and a gas hourly space velocity of 400 to 7,500 hr−1.
Moreover, U.S. Pat. Nos. 6,239,057 and 6,426,442 disclose a process for producing higher carbon number hydrocarbon(s), e.g., benzene, from low carbon number hydrocarbon(s), such as methane, by contacting the latter with a catalyst comprising a porous support, such as ZSM-5, which has dispersed thereon rhenium and a promoter metal such as iron, cobalt, vanadium, manganese, molybdenum, tungsten or a mixture thereof. After impregnation of the support with the rhenium and promoter metal, the catalyst is activated by treatment with hydrogen and/or methane at a temperature of about 100° C. to about 800° C. for a time of about 0.5 hr. to about 100 hr. The addition of CO or CO2 to the methane feed is said to increase the yield of benzene and the stability of the catalyst.
WO 03/000826 and U.S. Patent Application Publication No 2003/0083535 disclose a system and method for circulating catalyst between a reactor system and a regenerator system. A circulating catalyst system includes a reactor system, a regenerator system, and a distribution unit. The reactor system and regenerator system are adapted to exchange catalyst. The reactor system preferably includes a fluidized bed riser reactor and the regeneration system preferably includes a regeneration zone adapted for the contact of catalyst with a regeneration gas. The system and method are adapted so that more than one regeneration gas may contact catalyst. The distribution unit is adapted to control the percentage of catalyst contacting each regeneration gas. Thus, the distribution unit is adapted to select the percentage so as to maintain the reactor system and regeneration system under a heat balance regime. Heat is preferably transferred from the regenerator system to the reactor system by an exchange of catalyst.
However, the successful application of reductive coupling to produce higher hydrocarbons, e.g., aromatic compounds, on a commercial scale requires the solution of a number of serious technical challenges. Examples of technical challenges are:
(a) the process is endothermic which requires high energy input;
(b) the process is thermodynamically limited, which requires high temperature operation to achieve high conversion;
(c) the process requires significant amount of make-up heat to compensate the energy requirement of the endothermic reaction and to maintain the high temperature required for high conversion;
(d) the process requires effective heat transfer and effective contact of light hydrocarbon(s) with the catalyst are required to achieve high conversion of methane;
(e) the process generates coke and/or catalyst coking at high temperature;
(f) the process may use feedstocks containing C2+ hydrocarbons in addition to methane, which feedstocks may increase coking of the catalyst used in the process; and
(g) to reduce problems related to catalyst attrition, it is desirable to minimize the circulation rate and other mechanical stresses on the catalyst.
Accordingly, there is a need to develop a process for converting methane to higher hydrocarbon(s), which provides high efficiency for heat transfer, adequate hydrocarbon/catalyst contacting, improved process conditions to maximize selectivity to desired higher hydrocarbons, e.g., aromatic compound(s), while minimizing coke formation, and minimizing of required catalyst circulation rates.